Photographic light-sensitive material containing a polymeric brightening agent

ABSTRACT

A photographic light-sensitive material containing, in at least one layer thereof, a polymer having the following recurring monomer units:   Where Ro is hydrogen, alkyl, aryl, hydroxyalkyl, alkoxyalkyl or sulfoalkyl, R1 and R2 are halogen,   M is alkali metal or ammonium, R and R&#39;&#39; are hydrogen, alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aralkyl or cycloalkyl, and A is -(CH2)4-, -(CH2)5-, -(CH2)2-O-(CH2)2- or -(CH2)2-S(CH2)2- R1 and R2, and R and R&#39;&#39; may be the same or different.

United States Patent Hiroyuki Amano; Nobuo Tsuji; Kazuo Shirasu; Yoshinori Tutiya, all of Kanagawa, Japan [72] Inventors [54] PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL CONTAINING A POLYMERIC BRIGHTENING AGENT 9 Claims, No Drawings [52] U.S. Cl 96/82,

96/84, 117/335 [51] Int. Cl G031: 1/92 [50] Field of Search 96/82, 84; 1 17/335 T- [56] References Cited UNITED STATES PATENTS 2,875,053 2/1959 7 Minsk 96/84 2,882,150 4/1959 Van Allen et al.. 96/11 3,047,390 7/1962 Koerber et al.. 96/82 3,127,270 3/1964 Wilson 96/1 14.7 3,181,948 4/1965 Koerber eta 96/82 3,269,840 8/1966 Pattyn et al..... 96/82 3,512,984 5/1970 Amano et al. 96/84 Primary Examiner-Ronald Hi Smith Attorney-Sughrue, Rothwell, Mion, Zinn & MacPeak ABSTRACT: A photographic light-sensitive material containing, in at least one layer thereof, a polymer having the following recal -ring monomer units:

Where R is hydrogen, alkyl, aryl, hydroxyalkyl, alkoxyalkyl or sulfoalkyl, R and R are halogen,

" SR, N and N A, /l

M is alkali metal or ammonium, R and R are hydrogen, alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aralkyl or eycloaly i and A is z)4 (CH2)5 Y '(CH2)2 0(CH2)2 or (Cl-1,),-S(Cl-1 R and R and R and R may be the same or different.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photographic light-sensitive material containing a high molecular weight compound having ultraviolet ray absorbing action and fluorescence brightening action.

2. Description of the Prior Art In general, when a color image consisting of an azomethine or an indoaniline dye is obtained by color developing and then the color image is exposed to ultraviolet rays, it is faded or discolored depending on the strength and wave length of the rays. As is well known, unfavorable stains are formed in a finished photographic layer by attacking with ultraviolet rays when coexistent materials, besides forming a color image (for example a coupler) remains in the photographic emulsion layer after the color image is formed. Such phenomenonis often caused by ultraviolet rays of 300 to 400 millimicrons in wavelength. For the purpose of preventing this, ultraviolet absorbers have often been incorporated in the photographic emulsion layer, intermediate layer, protective layer, subbing layer, or the back of the support. However, many of the known ultraviolet absorbers have such disadvantages that the absorber itself tends to cause photolysis by ultraviolet rays, thus resulting in unfavorable stains, or a large part thereof diffuses out in the steps of photographic processing and washing with water so that its effect is weakened.

It has been customary, heretofore, as a means for brightening a photographic printing paper, to add a fluorescent brightening agent. The agents are capable of emitting violet to blue fluorescence, during ultraviolet radiation, to a photographic light-sensitive emulsion layer including a positive layer of printing paper, by the diffusion transfer and reversal method, or to an auxiliary layer such as subbing layer, protective layer or baryta layer of baryta paper. However, many commercial fluorescent brightening agents encounter the disadvantage that most of the brightening agent diffuses out in the steps of photographic processings and washing, as in the case of the ultraviolet absorber, thus losing the brightening effect, since it is hard to dye on a colloid of a photographic emulsion layer or auxiliary layer, for example, gelatin, due to its low molecular weight,

Since then, various efforts have been made in order to overcome the foregoing disadvantages, such as, by introducing a substituent excellent in dyeing affinity to gelatin, and by dispersion in a gelatin-polyvinylpyrrolidone (Japanese Pat. publication No. 7127/59 or poly-N-vinyl-S-methyl-Z- oxazolidinone (Japanese Patent publication No. 22065/64 The substituent has excellent dyeing affinity to fluorescent brightening agents, but in these methods, diffusing-out of a fluorescent brightening agent cannot be prevented enough, and the brightening effect decreases considerably.

SUMMARY OF THE INVENTION It is an object of the invention to provide a photographic light-sensitive material having a marked ultraviolet ray inhibiting effect as well as a stain preventing effect.

It is another object of the invention to provide a photographic light-sensitive material having a marked fluorescent brightening effect.

DESCRIPTION OF THE INVENTION These objects can be achieved by incorporating a polymer in at least one layer of a photographic light-sensitive emulsion layer and photographic auxiliary layer, such as intermediate layer, protective layer, subbing layer, including baryta layer of baryta-coated paper, back layer, etc. The polymers are homopolymers or copolymers having a recurring unit represented by the following formula:

wherein R represents a hydrogen atom, an alkyl group having from one to eight carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl,'octyl, etc., an aryl group having from six to 12 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, etc., a hydroxyalkyl group having from two to four carbon atoms such as hydroxyethyl, hydroxypropyl, etc., an alkoxyalkyl group having from two to six carbon atoms such as methoxyethyl, ethoxyethyl, a sulfoalkyl group having from one to four carbon atoms such as sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl or an alkali metal, or ammonium salt thereof such as sodium, potassium, ammonium, etc. R, and R, may be the same or different and each represents a halogen atom, OR, SR,

R N ,or 1 :I R

wherein R and R may be the same or different and represent a hydrogen atom, an alkyl group having from one to l2 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl,: dodecyl, etc., a hydroxyalkyl group having from one to four carbon atoms such as hydroxyethyl, hydroxybutyl, etc., a sulfoalkyl group having from one to four carbon atoms, an alkali metal or ammonium salt thereof, a carboxyalkyl group having from one to four carbon atoms such as carboxymethyl, carboxyethyl, carboxybutyl, etc., an alkali metal or ammonium salt thereof, an aralkyl group having from seven to l4 carbon atoms such as benzyl, etc., an aryl group having from six to 18 carbon atoms such as phenyl, tolyl, hydroxyphenol, chlorophenyl, carboxyphenyl, sulfophenyl, naphthyl, carboxynaphthyl, sulfonaphthyl', etc., a cycloalkyl group having from six to [0 atoms such as cyclohexyl, etc., or a heterocyclic group such as pyridyl, benzothiazolyl, etc., and, A represents (CH2)4 2)s 1 (CH2)20'(CH2)20I' (CH2)2 -S (CH M represents an alkali metal such as sodium, potassium etc., or an ammonium group,

A monomer unit which constructs the copolymer used in the present invention is represented by the following formula:

oiimromon, CONH2 CONHCH CON(Cl-l CHgCH OHgO 1 CON l \(|.IICH1 Although the preferred copolymers have a monomer unit as defined by formula II, the copolymer used in the invention may have any other monomer units that are copolymerizable therewith. The polymers used in the present invention are characterized by having the recurring unit represented by the o a ,W

By incorporating the above-mentioned high molecular Weight compound of the inventiofl in y of the y? of 5 can readily be obtained by the stepwise reaction of a derivaphotographic g -sens ti material, a marked ultlavlolet r y tive of 4,4'-diaminostilbene-2,2-disulfonate with a suitable absorbing effec an ain pr v n g efiecl can be g en, and derivative of cyanuric chloride in a conventional manner, as is there is no stain even under a strong ultraviolet radiation. The disciosed in y i Gosei Kagaku Kyokaishi (Bulletin f o high molecular weight compounds used in the invention have ganic Synthetic Chemistry Association) Vol. 20, page 64 remarkable brightening effects on photographic printing to 1962). p per eing h l n f r h steps of ph gr phi The ratio ofreaction of compound (III) to polyvinyl alcohol processings an W hingor its copolymer is not particularly limited, but, considering Addition of an ultraviolet ray absorbing material, in general, the re e t of economy and fluorescent strength, it is not alis carried out by a dir t additi n m th d using Wat r or a ways necessary to react it with all the vinyl alcohol units. For vent as a dissolving medium or by an indirect addition method in tance, it is desirable, in order to obtain good fluorescent using a high boiling point solvent as a dispersing or emulsifying strength, that compound lll be linked with polyvinyl alcohol medium, It is generally desirable that the ultraviolet ray abin such a manner that dispersion can be effected to an extent sorbing material be in the uppermost layer, but, in the case of that no concentration quenching occurs. As a result of our exa light-sensitive material produced by the latter method, this is periments it was unexpectedly found that a polymer subnot as necessary, since the added material tends to segregate stituted with compound (III) in a proportion of 0.1 to 50 mole by shock or friction. On the contrary, the compound of the inpercent, particularly, 0.5 to 10 mole percent, based on the vention may be incorporated in the uppermost layer by the vinyl alcohol unit, is sufficiently effective. direct addition method. Illustrative of the polymer used in the invention are com- Synthesis of the high molecular weight compound of the inpounds having the following recurring units: vention is generally carried out by dissolving or dispersing a compound of the triazylaminostilbene type represented by following formula III in polyvinyl alcohol or a copolymer thereof with a solvent such as water or dimethylformamide, adding Compound w thereto an aqueous solution of caustic soda in an amount -cH, 0H- equivalent to, or somewhat in excess of, that of the compound 0H 1]] and reacting them at a temperature of 50l50 C. l

A t N t l l 3 5 HN- NH 7 CH=CH-NHL ,J-NH N I N N I J I L soma SOaNa no .4 M do M R0 111 Compound 2. M.W.= 150,000 -cH,- JH- CH;HN \N NH -CH=CH-NH N NHCH;

S03NB SOQNB Compound 3.M.W.= 200,000

\ CH -([]H- lynomornon I N/\|N l| HN-' )NHCH=CH-/ NH- NII N N l CHgCHgOH HjCHgOH SOzNa SOzNa Compound 4.-M.W.= 300,000 CH (|3H in which R R R and M have the same meaning as in the formula 1. Of course, the synthesis is not limited to the abovementioned methgd. V

The cyanuric chloride derivative represented by formula III SOgNti SO Na 3 ,6 1 5 ,544 7 8 Compound 12.M.W.= 200,000 '(CHICI7H)5(CH:?H)05 SO;Na SOQNB o 011 OCOCH; n;

l SOINB SO3N8 Compound 14.M.W.= 150,000 (CHgCH)5(CHz-?H)ns Compound 15.--M.W.=200,000

Although the larger the molecular weight of the high more particularly about 100,000-400,000 is preferably used. molecular weight compound used in the invention, the better The photographic emulsion used in this specification means the prevention of dissolving out in photographic processing, the commonly used light-sensitive silver halide emulsion, but, the need for a lack ofsolubility can be satisfied if polyvinyl al- 70 as a colloidal agent for such emulsions, not only gelatin, but

cohol or its copolymer, as a trunk polymer, has a degree of also synthetic resins such as polyvinyl alcohol and polyvinyl polymerization of more than about 50 or a molecular weight acetal can favorably be used. of more than about 20,000. The following examples are given in order to illustrate the In the present invention, the high molecular weight comresults about the light fading absorbing effect of an image, dif- Pound a g o ecul Weight Ofabout 9 9 000, 75 fusion resistance and fluorescent brightening and a photowas coated thereon (thickness: 2.0 microns.) The protective graphlc prmting paper 1n mstances where the high molecular layer was prepared by gradually adding 1 .kg. of an aqueous welght g pp Qfthe mvemlon is used Without hmmng solution of gelatin to 100 g. of a 4 percent solution of each of Scope t e mvemlonr the high molecular ultraviolet inhibiting materials of the invention, m EXAMPLE co pound l-compound l6, 1n dimethylformamlde water (l:l,) coating and drying.

1 kg. of a4percent aqueous solution of gelatin was gradually Then, the thus p p ed 1 P i ing P per was subjected added to 100 g. of a 4 percent solution of the high-molecular to exposing, de e op ng ith a developing solution containing ultraviolet absorbers of the invention, compound l-com- N-ethyl-N-B-hydroxyethyl-p-phenylenediamine, st p-fi i g. pound l6, and a known low molecular weight ultraviolet abwashing, bleach-fixing, washing, hardening, washing and drysorber, compound 17, in water-dimethylformamide (1:1). ing. The fading ratio at an image density of 1.0 is shown in the Compound 17 (for comparison) following table, when the coated paper was exposed by means i N SO;Na SOsNa l I OH OH The emulsions were coated onto film supports and dried to of a Xenon tester for hours. The Xenon tester used in this prepare 8 filter laye ha ing a Ih kn S OfZ-O mi r n The fading test was a light source having a strength and spectrum di so ing-out e c o t e compoun s measured on the thus distribution of energy very similar to the spectrum distribution resultlng filters 1s tabulated below. of the daylight energy.

Addi'ive Dccfcsc of optical i y p.) Fading ratio of color image after being exposed for 20 hours by Xenon tester.

Process Water water 3% aqueous overall photowashing washing NA,CO graphic pro- Additive Cyan Color image Yellow solution cessing Magenta Time 30 min. 2 hours 30 min. 25 min. Compound I 10%25: l i Compound 2 I25 2% l3'i Compound 3 I09} 2% ll; gmnpmmdl 9% 9% Compound4 10% 2% 11% ompouncl 2 lll l3l 1 l2; l2; Com d a 10% 12 1 11% 11% 5 w 0 poun Com d4 5% 6q 6% Compound l2; 2% l3;

poun 6% Compound 5 0 2% I; 0 Compound 7 8% I; 9; Com ound 6 13% 15% 14% 14% 8 I m P Corn 0 nd 7 3'1 4% 4% 1; mpou d 9 8% 1% 9 p u Compound 8 0 2% 0 0 Compound 10 12 21 ISX Com ound ll 8% 1% 9% Compound 9 2% a; 3; 2% ND g Compound 10 12% 14% 13% 13% Compound 11 2% 3% a; an 40% Compound 12 10; 12st 11% 11; Compound l3 l3Z HQ 14' 14% 5 comvound 14 In 13% As is evident from the test results, fading ofa color image in Compound l5 IOZ lZ'K lli H; h It i l b b ddeclt tect-v Compound '6 a In In a case w ere no u ra 10 e a sor er 1s a o a pro 1e Compound [7 355 layer can be reduced by the use of the ultrav1olet absorber of the invention. In instances where such ultraviolet absorbing 5O layer is not used for a protective layer but is used for an intermediate layer between a first emulsion layer and second emulsion layer, as well as, between a second emulsion layer and third emulsion layer, the fade preventing effect on the color image appears in the layer under the intermediate layer containing the ultraviolet absorber, as expected.

In the case of using a film base as a support in place of the baryta paper, substantially similar results were obtained The stain preventing effect of the thus provided and processed color printing paper is shown in the following table, in which the stain is represented by the increase of density of the yellow component in the nonexposed area when using a Xenon tester as an ultraviolet light source.

It is apparent from these results that the high molecular weight compounds of the invention, compounds l-l6, are only slightly dissolved out and very diffusion resistant while a low molecular weight, diffusible substance, such as known compound 17, almost completely dissolves out from a gelatin 55 layer in the steps of photographic processing and washing. The overall photographic processings designated herein involve the steps of developing, stop-fixing, washing, bleach-fixing, washing, hardening, washing and drying, ordinarily used in color photography.

Each of the high molecular weight compounds used in the invention gave a similar effect to the above-mentioned when having a limit viscosity [1710f 0.1 to 2.0 in a solvent of dimethylformamide-water 1:1 at 30 C.

A blue-sensitive silver iodobromide emulsion containing v 3,5-di-carboxy-a-(4-stearoylamidebenzoyl) acetanilide, yel- Add: Wm Expm" low coupler was coated onto a baryta paper. The coupler was added as an alkaline aqueous solution. Then, a green-sensitive 222K233; 3'3 2:: silver chlorobromide emulsion containing 1( 3-sulfo-4- comsound 3 phenoxyl)-3-stearoyl-S-pyrazolone, magenta coupler and Compound 4 0.11 012 further a red-sensitive silver chlorobromide emulsion contain- '"P"" 5 ing N-n-octadecyl-l-hydroxy-4-sulfo-2-l-naphthamide, cyan 2:252:23: 31:; 3:}:

coupler were coated thereon and further a protective layer Compound 8 0.11 0.12

Table Continued Compound 9 0.11 0.12 Compound 10 0.11 0.12 Compound 11 0.11 0.12 Compound 12 0.09 0,12 Compound 13 0.09 0.12 Compound 14 0.09 0.12 Compound 15 0.09 0.12 Compound 0.09 0.12 No additive 0.13 0.20

It will be apparent from these test results that the stain preventing effect can be given by adding the high molecular weight compound of the invention to a protective layer. The brightening degree of a color printing paper can be improved more markedly by adding the high molecular weight compound of the invention, as compared with the case of using no additive.

EXAMPLE Ill The first emulsion layer of example 11, i.e., 1 kg. of the redsensitive silver chlorobromide emulsion was gradually added to 50 g. of a 4 percent solution of each of the high-molecular weight ultraviolet preventing materials of the invention, compound lcompound 1 l in dimethylformamide-water (1:1) and mixed completely, to which the cyan coupler was added (thickness: 4.0 microns). The magenta layer as a second layer and the yellow layer as a third layer were the same as those of example 11.

The thus prepared multiemulsion layer sensitive materials were subjected to exposing, developing, stop-fixing, washing, bleach-fixing, washing, hardening, washing and drying and the fading ratio at a color image density of 1.0 was measured after exposure for 20 hours by means of a Xenon tester to obtain the following results.

Fading ratio of color image after being exposed for 20 hours by Xenon tester Additive Cyan Magenta Yellow Compound 1 22% 2% 12% Compound 2 25% 2% 14% Compound 3 23% 2% 13% Compound 4 22% 2% 12% Compound 5 13% 8% Compound 6 25% 2% 15% Compound 7 17% 1% 10% Compound 8 14% 1% 8% Compound 9 18% 1% 10% Compound 10 25% 2% 15% Compound 11 16% 1% 11% No additive 40% 20% 40% It will be apparent from the test results that a very large ultraviolet preventing effect can be given by adding the high molecular weight ultraviolet preventing material of the invention directly to an emulsion even though providing no particular ultraviolet preventing layer.

EXAMPLE IV Fading ratio of color image after eing exposed for 20 hours by Xenon tester lo Additive Cyan Magenta Compound 1 Compound 2 Compound 3 Compound 4 Compound Compound 6 Compound 7 Compound 8 Compound 9 Compound Compound 11 No additive As is evident from the test results, fading of a color image in a case where no ultraviolet absorber is added to a subbing layer (lowermost filter layer) can be prevented or reduced by the use of the ultraviolet absorber of the invention. In instances where such an ultraviolet absorbing layer is provided not on a subbing layer but on the back of the support, a substantially similar fade preventing effect was obtained Moreover, where the ultraviolet absorber of the invention is added to a protective layer and a subbing layer or on the back of the support, also, a substantially similar fade preventing effeet to light from the emulsion surface, as well as light from the back of the support appears.

EXAMPLE V 10 g. of a 4 percent solution of each of the high molecular weight compounds of the invention, compound l-compound 16, in dimethylformamide-water (1:1) was gradually added to 1 kg. of a chlorobromide emulsion for enlargement, mixed with a necessary hardener and wetting agent, and coated onto a baryta paper. The thus prepared printing paper held the same brightening degree as the nonprocessed paper, while another printing paper prepared by the use of the known low molecular material, compound 17 lost a substantial'amount of brightness after the steps of developing, fixing and washing.

What is claimed is: 1. A photographic light-sensitive material containing a silver halide emulsion layer and in which a polymer having recurring units represented by the following formula is incorporated into at least one layer on said material.

wherein R represents a member selected from the class consisting of a hydrogen, an alkyl group having from one to eight carbon atoms, an aryl group having from six to 12 carbon atoms, a hydroxyalkyl group having from two to four carbon atoms, an alkoxyalkyl group having from two to six carbon atoms, a sulfoalkyl group having from one to four carbon atoms, and alkali metal salts and an ammonium salt of said sulfoalkyl group, R and R represent a member selected from the class consisting of, halogens,OR,-SR,

R N and a cycloalkyl group having from six to 10 carbon atoms, said R 15 and and R being the same or different; and A represents a member selected from the class consisting of (CH 2)5 2)2 2)2 2)2 2)2 said R, and R being the same or different, and M represents a member selected from the class consisting of al- 20 kali metals and ammonium.

2. A photographic light-sensitive material as claimed in claim 1, wherein said polymer is a copolymer, and additionally contains at least one recurring unit represented by the following formula:

wherein X represents a member selected from the class consisting of OH, OCH;,, OCH CH OCl-l CH Ol-l, OCOCH OCOCH CH -OCONH OCOHNCH OH, CONH 'CONHCH CON(CH 3. A photographic light-sensitive material as claimed in claim 1, wherein said polymer has a recurring unit selected 25 from the class consisting of,

CHzCHzOH IIIHCHjCHZOH S OaNa 803N8- sioma sotNa S OaNa S OaNa CH: o=o

s o N SOJNB SOzNa so 4. The photographic light-sensitive material as claimed in claim 1, wherein said polymer has a molecular weight of from claim 2, wherein said recurring units of claim 1 are present in 20,000 to 1,000,000. an amount of from i0 50 mole P based on the 7. The photographic light-sensitive material as claimed in P y backbone unitsclaim 6, wherein said molecular weight is from 100,000 to 5. The photographic light-sensitive material as claimed in 8. The photographic light-sensitive material as claimed "I claim 4, wherein said recurring units of claim 1 are present in claim 1, wherein said recurring units have the formula:

(M.W.=400, 000) CH1?H- O OH "a -i Pf 9. The photographic light-sensitive material as claimed in 6. The photographic light-sensitive material as claimed in claim 1, wherein said recurring units have the formula:

l SOaNa SO Na 

2. A photographic light-sensitive material as claimed in claim 1, wherein said polymer is a copolymer, and additionally contains at least one recurring unit represented by the following formula: wherein X represents a member selected from the class consisting of -OH, -OCH3, -OCH2CH3, -OCH2CH2OH, -OCOCH3, -OCOCH2CH3, -OCONH2, -OCOHNCH2OH, -CONH2, -CONHCH3, -CON(CH3)2,
 3. A photographic light-sensitive material as claimed in claim 1, wherein said polymer has a recurring unit selected from the class consisting of,
 4. The photographic light-sensitive material as claimed in claim 2, wherein said recurring units of claIm 1 are present in an amount of from 0.1 to 50 mole percent, based on the polymer backbone units.
 5. The photographic light-sensitive material as claimed in claim 4, wherein said recurring units of claim 1 are present in an amount of from 0.5 to 10 mole percent.
 6. The photographic light-sensitive material as claimed in claim 1, wherein said polymer has a molecular weight of from 20,000 to 1,000,000.
 7. The photographic light-sensitive material as claimed in claim 6, wherein said molecular weight is from 100,000 to 400,000.
 8. The photographic light-sensitive material as claimed in claim 1, wherein said recurring units have the formula:
 9. The photographic light-sensitive material as claimed in claim 1, wherein said recurring units have the formula: 